Hydrorefining of crude oils



United States Patent 3,196,104 HYBROREFINHQG GE (IRUDE GILS William K.'i. Eleim, Island Lake, and Joseph T. Ari-ago, Mount lrospect, Illassignors to Universal Eli! Products Company, Des ilaines, ill.., acorporation of Delaware No Drawing. Filed .luly 2, 1962, Ser. No.207,069 16 Claims. Ci. fits-464) This invention relates to a novelprocess for hydrorefining petroleum crude oils, heavy vacuum gas oils,heavy cycle stocks, etc, and to a novel catalyst especially adaptedthereto. More specifically, the present invention involves a process forhydrorefining heavy hydrocarbon charge stocks to effect the removal ofnitrogen and sulfur therefrom, and affords unexpected advantages whenemployed for the removal of metal contaminants and/ or the conversion ofpentane-insoluble asphaltenes into pantane solu ble hydrocarbon oils.

Crude petroleum oils, and also the heavier hydrocarbon fractions and/ordistillates derived therefrom, generally contain considerable quantitiesof sulfurous and nitrogenous compounds. in addition, the crude oils, andthe heavy hydrocarbon fractions thereof, contain certain metalliccontaminants which have an adverse effect on the activity of catalystsutilized in various processes to which crude oils, or heavy hydrocarbonfractions thereof, are ultimately subjected. The most common metalliccontaminants are nickel and vanadium, although other metals includiniron, copper, etc., are often present. These metals occur in a varity offorms. They may exist as metal oxides or sulfides introduced into thecrude oil as metallic scale or similar particles, or they may exist inthe form of Water-soluble salts of such metals. Usually, however, theyexist in the form of thermally stable organo-metallic compounds, such asmetal porphyrins and the various derivatives thereof.

Although the metallic contaminants existing in the form of an oxide orsulfide scale may be separated, at least in part, by relatively simplefiltering techniques, and the water-soluble salts are at least in partremovable by Washing and subsequent dehydration, more extensivetreatment is required to remove the thermally stable organometalliccompounds before the crude oil or heavy hydrocarbon charge is suitablefor further processing.

In addition to the thermally stable organometallic compounds, crude oilscontain greater quantities of sulfurous and nitrogenous compounds thanare found in lighter hydrocarbon fractions such as gasoline, kerosene,light gas oil, etc. For example, a Wyoming sour crude, having a gravityof 232 API at 60 F., contains about 2.8 Wt. percent sulfur and about2700 p.p.m. of total nitrogen. Reduction in the concentration of thesulfurous and mitrogenous compounds to the extent that the crude oil orheavy hydrocarbon charge is suitable for further processing, isaccomplished with little difficulty by conversion thereof to hydrogensulfide and ammonia which are readily removed from the system in agaseous phase. However, reduction in the concentration of the thermallystable organometallic compounds to the extent that the crude oil orheavy hydrocarbon charge is suitable for further processing, is not asreadily achieved. Although the concentration of the thermally stableorganometallic compounds is relatively small, for example, often lessthan about p.p.rn. calculated as the elemental metal, subsequentprocessing techniques are adversely affected thereby. For example, whena hydrocarbon charge stock containing metallic contaminants in excess ofabout 3 ppm. is subjected to catalytic cracking, the metals becomedeposited on the catalyst, altering the composition thereof to theextent that undesirable by-products are formed. That is to say, thecomposition of the catalyst, which is closely 3,l%,ld Patented July 20,1963 controlled with respect to the nature of the charge stock beingprocessed and the quality and quantity of the product desired, isconsiderably changed as a result of the metal deposition theron duringthe course of the cracking process. As a consequence the liquid productrecovery is reduced, and coke and hydrogen are formed in excessiveamounts, the former producing relatively rapid catalyst deactivation.The presence of thermally stable organometallic compounds, includingmetal porphyrines, has an adverse effect on other processes includingcatalytic reforming, isomerization, hydrodc-alkylation, etc.

in addition, crude oils and other heavy hydrocarbon fractions generallycontain large quantities of pentaneinsoluble materials present in theform of a colloidal suspension or dispersion difiicult of effectivecontact with conventional hydrorefining catalysts. Thesepentane-insoluble materials, described as asphaltenes, are carbonaceousmaterials considered as coke precursors having a tendency to becomeimmediately deposited Within the reaction zone and on the catalyticcomposite as a gummy hydrocarbonaceous residue. It is further consideredthat said asphaltenes contain the bulk of the difiiculty removable metalcontaminants as well as a considerable portion of the nitrogenous andsulfurous compounds.

The object of the present invention is to provide a process forhydrorefining heavier hydrocarbonaceous materials, particularlypetroleum crude oils, utilizing a catalyst formed in a particularmanner. In other hydrorefiniug processes, the metals contained Withinthe crude oil charge stock are removed therefrom by deposition of thesame on the hydrorefining catalyst employed. This practice greatlyincreases the amount of catalyst in a very short time, precluding theuse of a fixed-bed catalyst system commonly employed in the present-dayrefining operations. Slurry processes, employing catalytioal ly activemetals deposited upon silica and/or alumina, are Very errosive, and makeplant upkeep diflicult and expensive. The present invention teaches thepreparation of a colloidally dispersed unsupported catalyst useful in aslurry type process, and which catalyst will not effect extensiveerrosion of the reaction system. The present process yields a liquidhydrocarbon product Which is more suitable for further processingWithout experiencing the difiiculties otherwise resulting from thepresence of the above-described contaminants. The process of the presentinvention is particularly advantageous in effecting the removal ofthermally stable organometallic compounds Without significant productyield loss, while simultaneously converting the pentane-insolublematerials into pentant-soluble liquid hydrocarbons.

In a broad embodiment, the present invention relates to a hydrorefiningcatalyst comprising the thermal decomposition product of anorganometallic complex obtained by the reaction of a halide of a metalof Groups 53, 6B, and the Iron Group with an oxygen-containing organiccompound.

in another broad embodiment, the present invention relates to a methodof preparing a hydrorefining catalyst which comprises admixing ahydrocarbon charge stock and an organometallic complex obtained by thereaction of a covalent halide of a metal of Groups 5B, 6B, and the IronGroup with an oxygen-containing organic compound, and heating saidmixture at a temperature of less than about 310 C. for a time sufiicientto decompose said organometallic complex.

In still another broad embodiment the present invention relates to aprocess for hydrorefining a petroleum crude oil which comprises admixingsaid crude oil and an organometallic complex obtained by the reaction ofa covalent halide of a metal Iron Group, with an oxygen-containingorganic compound, and heating said mixture at a temperature of of Groups5B, 6B, and the.

less than about 310 C. for a time sufiicient to decompose saidorganometallic complex, reacting the resulting colloidal suspension withhydrogen at a temperature in excess of about 225 C. and at a pressure inexcess or about 500 p.-s.i.g., and recovering the resulting hydrorefinedpetroleum crude oil.

From the foregoing embodiments it is readily ascertained that theprocess of this invention involves the utilization of a novelhydrorefining catalyst comprising the thermal decomposition product ofan organometallic complex. The organometallic complex of the presentinvention' is the reaction product of a halide of a metal of Groups 53,6B, and the Iron Group of the Periodic Table (Handbook of Chemistry andPhysics, 43rd ed.), preferably a covalent halide of said metals, and anoxygen-containing organic compound including, for example, an organicacid, anhydride, ester, ether, alcohol, ketone, aldehyde, and the like.The aforementioned oxygen-containing organic compound can be aliphaticor cyclic, containing up to about 20 carbon atoms, and with carbon tocarbon saturation or unsaturation. Suitable oxygen-containing organiccompounds thus include the various structural isomers of methanoic acid,ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, etc., andhigher homologs thereof, as well as Z-propenoic acid, Z-butenoic acid,3-butenoic acid, 2pentenoic acid, etc., and also includingcyclopentanecarboxylic acid, cyclohexanecarboxylic acid, and the like.Suitable oxygencontaining organic compounds also include the variousanhydrides of the aforementioned acids, for example, ethanoic anhydride,propanoic anhydride, butanoic anhydride, etc. Said oxygen-containingorganic compound may be an aldehyde such as, for example, the variousstructural isomers of methanal, ethanal, propanal, butanal, pentanal,etc., and higher homologs thereof, and also 2-propenal, Z-butenal, etc.,or a ketone including Z-propanone, Z-butanone, Z-pentanone, 3-pentanone,3-penten- 2-one, cyclopentanone, cyclohexanone, etc. Ethers, such asmethyl ether, ethyl ether, methyl ethyl ether, propyl ether, butylether, pentyl ether, hexyl ether, and the like, as well as furan, pyran,etc., are suitable oxygen-containing organic compounds. Alcohols,including the various structural isomers of methanol, ethanol, propanol,butanol, pentanol, hexanol, 4-penten-1-ol, cyclopentanol, cyclohexanol,etc., and also esters of the aforementioned acids, for example, methylacetate, ethyl acetate, propyl acetate, butyl acetate, etc., are alsosuitable oxygen-containing organic compounds.

The aforementiioned halide of a metal of Groups 513, 6B and the IronGroup can be a halide of vanadium, niobium, tantalum, molybdenum,tungsten, chromium, iron, nickel, or cobalt, and preferably a covalenthalide of said metals. Suitable metal halides thus include vanadiumtrichloride, vanadium tetrachloride, vanadium pentachloride, vanadiumoxychloride, vanadium oxydichloride, vanadium oxytrichloride, niobiumtrichloride, niobium pent-achlonde, niobium oxytrichloride, tantalumpentachloride, molybdenum dichloride, molybdenum trichloride, molybdenumtetrachloride, molybdenum pentachloride, molybdenum oxytrichloride,molybdenum oxytetrachloride, molybdenum dioxydichloride, molybdenumtrioxypentachloride, tungsten dichloride, tungsten tetrachloride,tungsten pentachloride, tungsten hexachloride, tungsten.oxytetrachloride, tungsten dioxydichloride, chromium dichloride,chromium trichloride, chromium dioxydichloride, ferrous chloride, ferricchloride, nickel chloride, cobaltous chloride, cobaltic chloride, etc.,as Well as the corresponding fluorides, bromides, and iodides of theaforementioned metals.

The halides of the metals of Groups 5B, 6B, and the Iron Group, of whichthe above enumerated halide are illustrative, react vigorously withoxygen-containing organic compounds of the class hereinabove described.During thecourse' of the reaction, which involves the abstraction of thehalogen atom of the metal halide and the cleavage of an oxygen-carbonbond, or an oxygen-hydrogen bond as the case may be, of theoxygen-containing organic compound, said compound combines with themetal portion of the aforesaid metal halide by means of the residualvalences created, to form the desired organometallic complex. Theorganometallic complex thus formed contains at least one metal from thegroup of vanadium, niobium, tantalum, chromium, molybdenum, tungsten,iron, nickel, and cobalt.

One preferred embodiment of this invention relates to a hydrorefiningcatalyst comprising the thermal decomposition product of anorganometallic complex obtained by reacting molybdenum pentachloride andethyl ether.

Another preferred embodiment relates to a hydrorefining catalystcomprising the thermal decomposition product or" an organometalliccomplex obtained by reacting vanadium trichloride and ethyl ether.

Still another preferred embodiment relates to a hydrorefining catalystcomprising the thermal decomposition product of an organornetalliccomplex obtained by reacting molybdenum pentachloride and acetic acid.

Yet another preferred embodiment of this invention relates to ahydrorefining catalyst comprising the thermal decomposition product ofan organometallic complex obtained by reacting molybdenum pentachlorideand propanone.

The organometallic complex of this invention may be prepared simply bymixing the selected metal halide with at least a slight excess of theselected oxygen-containing organic compound. The reaction can beeffected at from about room temperature to about the boiling point ofthe particular oxygen-containing organic compound employed. Or thereaction may be effected in the presence of an inert solvent, such as achlorinated hydrocarbon, in which case the reaction mixture can beheated at about the boiling point of said solvent. On completion of thereaction, indicated by complete solution of the metal halide, the excessoxygen-containing organic compound and solvent is evaporated ordistilled from the desired organometallic complex.

The catalyst is formed by initially dissolving the organometalliccomplex in the hydrocarbon charge stock containing contaminatinginfluences, including pentane-insoluble asphaltenes which are to beconverted into pentane solublehydrocarbons. The quantity of theorganometallic complex employed is such that the colloidal suspension ordispersion, resulting when the complex is thermally decomposed in thehydrocarbon charge stock, comprises from about 1.0 wt. percent to about10.0 wt. percent calculated as the elemental metal. The resultingmixture is heated at a temperature less than about 310 C. for a timesufficient to effect decomposition of the organometallic complex,thereby forming the catalyst as a colloidal suspension or dispersionwithin the hydrocarbon charge stock. It is preferred that the aforesaidmixture be thus heated in an atmosphere substantially free of hydrogen.The presence of free hydrogen during the decomposition of theorganometallic complex tends to have an adverse effect on catalystactivity with respect to the conversion of the pentaneinsoluble fractionand removal of the thermally stable organometallic compounds such asporphyrins. The colloidal suspension or dispersion is then charged intoa suitable reaction zone maintained at a temperature of from about 225C. to about 500 C., and at a hydrogen pressure of from about 500 toabout 5000 pounds per square inch gauge.

The process of this invention may be efected in any suitable manner andmay comprise either a batch or a continuous type of operation. Forexample, when a batch type of operation is employed, hydrogen and thepetroleum hydrocarbon containing a decomposed organometallic complex arecharged to an enclosed vessel and maintained therein at the desiredtemperature and pressure and with stirring. On completion of thehydrorefining process the normally liquid hydrocarbons are separatedfrom the reaction mixture by any suitable means, for example, throughthe use of a settling tank or by means of a centrifuge, the resultingcatalyst sludge being recovered for reuse as such, or converted back tothe organometallic complex by any of the well-known chemical means. Theammonia and the hydrogen sulfide, resulting from the destructiveconversion of sulfurous and nitrogenous compounds contained within thepetroleum crude oil, are removed in a gaseous phase along with any lightparatfinic hydrocarbons such as methane, ethane, propane, etc. In acontinuous type of operation, the starting material comprising hydrogenand the colloidal suspension, are continuously charged to a reactormaintained at the proper conditions of temperature and pressure. Thereaction product is continuously withdrawn from the reactor at a ratewhich will insure an adequate residence time therein. The normallyliquid hydro carbons may be separated from the reactor efiluent in theabove described manner and the catalyst sludge recycled as a portion ofthe charge to the aforesaid reactor.

Although the hydrorefining process of the present invention is conductedin the presence of hydrogen, it is preferred that the decomposition ofthe organometallic complex be efiected in the absence thereof. Thedecomposition of the organometallic complex is conducted at atemperature less than about 310 C. in order to avoid ini tial crackingof the petroleum crude oil prior to effecting complete decomposition ofthe organometallic complex.

The following example are presented to illustrate the process of thepresent invention and the efiectiveness there of with relation to theconversion of sulfurous and nitrogenous compounds into sulfur-free andnitrogen-free hydrocarbons, the conversion of pentane-insolubleasphaltenes into pentane-soluble hydrocarbons, and the removal of nickeland vanadium from a petroleum crude oil. It is not intended that thepresent invention be unduly limit ted to the catalyst, charge stock,and/ or operating conditions employed within the example.

Example I The crude oil employed to illustrate the benefits affordedthrough utilization of the present invention, was

21 Wyoming sour crude oil having a gravity of 232 API at 60 F. The crudeoil contained 2.8 wt. percent sulfur, approximately 2700 ppm. ofnitrogen, 18 ppm. of nickel and 81 ppm. of vanadium as metal porphyrinscomputed as the elemental metal. In addition, the sour crude consistedof 8.3 wt. percent pentane-in soluble asphaltenes. As hereinafterindicated, the process of the present invention effects the conversionof a significant proportion of such asphaltenes to the degree that thesame no longer exert a detrimental effect upon further processmg.

An organometallic complex was prepared by slowly adding 180 g. ofmolybdenum pentachloride to about 1 liter of ethyl ether, and dissolvingsaid molybdenum pentachloride therein. Thereafter, the excess ether wasevaporated over a steam bath to yield a brown oil reaction product whichwas heated an additional two hours over the aforesaid steam bath. Thisbrown oil reaction product of molybdenum pentachloride and ethyl etherwas mixed with about 3000 g. of crude oil and the resulting mixture wasstirred at a temperature of about 275 C. for a 1 hour period.Thereafter, the mixture was cooled and passed through a colloidal mill.

The resulting colloidal suspension was charged to a reactor consistingof a high pressure vibromixer at the rate of about 125 cc. per hour fora liquid hourly space velocity of about 0.2, and in admixture with about35,000 c.f./bbl. recycle hydrogen. The reactor was maintained at about2000 p.s.i.g. and 430 C. The reactor effluent was centrifuged and thenormally liquid hydrocarbons recovered. The hydrorefined product,consisting of normally liquid hydrocarbons, contained about 347 ppm. ofnitrogen, 0.69 wt. percent sulfur, 0.134 wt. percent asphaltenes andless than 0.03 ppm. of nickel, 0.03 ppm. of vanadium, and 0.1 ppm. ofmolybdenum.

Example 11 800 g. of molybdenum naphthenate, comprising about 5 wt.percent molybdenum, which can be described as a reaction product ofnaphthenic acids and molybdenum pentachloride, was mixed with about4,000 g. of Wyoming sour crude oil and said mixture was diluted withabout 4,000 g. of a vacuum gas oil having a gravity of 22.1 API and aboiling range of 600-950" F. at an absolute pressure of 0.20 mm. Hg. Theresulting mixture contained 2.40 wt. percent sulfur, 2,096 p.p.m. ofnitrogen, 4.45 wt. percent asphaltenes, 36.8 ppm. of vanadium, 10.9 ppm.of nickel, and 1800 p.p.m. of molybdenum. This mixture was stirred at atemperature of about 275 C. for a one hour period. The resultingcolloidal suspension was charged at the rate of about 110 g./hour to areactor consisting of a high pressure vibromixer for a liquid hourlyspace velocity of approximately 0.21, and in admixture with about 35,000c.f./bbl. recycle hydrogen. The reactor was maintained at a pressure ofabout 2,000 p.s.i.g. and at a temperature of about 430 C. The reactoreflluent was centrifuged and the normally liquid hydrocarbons separatedtherefrom. The hydrorefined product, consisting of said normally liquidhydrocarbons, contained about 555 p.p.m. of nitrogen, 0.38 wt. percentsulfur, 0.079 wt. percent asphaltenes, and less than 0.04 ppm. ofnickel, 0.01 ppm. of vanadium, and 0.1 ppm. of molybdenum.

Example Ill An organometallic complex was prepared by slowly adding 6 g.of molybdenum pentachloride to about 20 g. of acetone (propanone) anddissolving said molybdenum pentachloride therein. Upon completion of thereaction the excess acetone was evaporated from the reaction product,which was a brown oil. This last mentioned reaction product ofmolybdenum pentachloride and acetone, comprising about 2.1 g. ofmolybdenum, was added to g. of Wyoming sour crude and the mixture heatedat about 220 C. to decompose the organometallic complex. The resultingcolloidal suspension was charged to an autoclave, pressured to 200atmospheres with hy drogen, and heated at 400 C. The autoclave wascontinuously rotated at these conditions for a period of 4 hours. Thereaction mixture was recovered from the autoclave and centrifuged toseparate the normally liquid hydrocarbons from the catalyst sludge. Thehydrorefined product, comprising the aforesaid normally liquidhydrocarbons, contained 234 ppm. of nitrogen and 0.48 wt. percentsulfur. A sour crude oil, hydrorefined in this manner, will contain lessthan about 0.5 wt. percent asphaltenes, and less than about 0.05 ppm. ofnickel, 0.01 ppm. of vanadium and 0.1 ppm. of molybdenum.

Example IV An organometallic complex was prepared by slowly adding 7 g.of vanadium oxytrichloride to about 50 milliliters of ethyl ether anddissolving said molybdenum pentachloride therein. On completion of thereaction the excess ether was evaporated from the reaction product whichwas a brown oil. This last mentioned reaction product of vanadiumoxytrichloride and ethyl ether, comprising about 2 g. of vanadium, wasadded to 100 g. of Wyoming sour crude and the mixture was heated atabout 220 C. to decompose the organometallic complex. The resultingcolloidal suspension was charged to an autoclave, pressured to 200atmospheres with hydrogen, and heated at 400 C. The autoclave wascontinuously rotated at these conditions for a period of 4 hours. Thereaction mixture was recovered from the autoclave and centrifuged toseparate the normally liquid hydrocarbons from the catalyst sludge. Thehydrorefined product, com prising the aforesaid normally liquidhydrocarbons, contained 879 ppm. of nitrogen and 1.3 wt. percent sulfur.

Z A sour crude oil, hydrorefined in this manner, will contain less thanabout 0.5 wt. percent asphaltenes, and less than about 0.05 ppm. ofnickel, 0.01 p.p.m. of vanadium and 0.1 ppm. of molybdenum.

Example V An organometallic complex was prepared by slowly adding 7 g.of vanadium tetrachloride to about 50 milliliters of ethyl ether anddissolving said vanadium tetrachloride therein. On completion of thereaction the excess ether was evaporated from the reaction product,which was a brown oil. This last mentioned reaction product of vanadiumtetrachloride and ethyl ether, comprising about 1.6 g. of vanadium, wasadded to 100 g. of Wyoming sour crude and the mixture heated at about220 C. to decompose the organometallic complex. The resulting colloidalsuspension was charged to an autoclave, pressured to 200 atmospheres ofhydrogen, and heated at 400 C. The autoclave was continuously rotatedat'these conditions for a period of 4 hours. The reaction mixture wasrecovered from the autoclave and centrifuged to separate the normallyliquid hydrocarbons from the catalyst sludge. The hydrorefined product,comprising the aforesaid liquid hydrocarbons, contained 865 ppm. ofnitrogen and 0.97 wt. percent sulfur. A sour crude oil, hydrorefined inthis manner, will contain less than about 0.5'wt. percent asphaltenes,and less than about 0.05 ppm. of nickel, 0.01 ppm. of vanadium and 0.1p.p.m. of molybdenum We claim as our invention:

1. A catalyst comprising the thermal decomposition product of anorganometallic complex obtained by the reaction of a halide of a metalselected from the group consisting of vanadium, niobium, tantalum,molybdenum, tungsten, chromium, iron, nickel and cobalt with an alkylether having from 1 to about 6 carbon atoms in each of its alkyl groups.

2,. A catalyst comprising the thermal decomposition product of anorganometallic complex obtained by the reaction of a covalent halide ofa metal selected from the group consisting of vanadium, niobium,tantalum, molybdenum, tungsten, chromium, iron, nickel and cobalt withan alkyl ether having from 1 to about 6 carbon atoms in each of itsalkyl groups.

3. A method of preparing a catalyst which comprises admixing ahydrocarbon charge stock and an organometallic complex obtained by thereaction of a covalent halide of a metal selected from the groupconsisting of vanadium, niobium, tantalum, molybdenum, tungsten,chromium, iron, nickel and cobalt with an alkyl ether having from 1 toabout 6 carbon atoms in each of its alkyl groups, and heating theresultant mixture at a temperature less than about 310 C. for a timesufficient to decompose said organometallic complex.

4. The method of claim 3 further characterized in that saidorganometallic complex is obtained by the reaction of a covalentmolybdenum halide with said ether.

5. The method of claim 3 further characterized in that saidorganometallic complex is obtained by the reaction of a covalentmolybdenum halide with ethyl ether.

6. The method of claim 3 further characterized in that saidorganometallic complex is obtained by the reaction of a covalentvanadium halide with said ether.

7. The method of claim 3 further characterized in that saidorganometallic complex is obtained by the reaction of a covalentvanadium halide with ethyl ether.

8. A process for hydrorefining a petroleum oil which comprises admixingsaid oil and an organometallic complex obtained by the reaction of acovalent halide of a metal selected from the group consisting ofvanadium, niobium, tantalum, molybdenum, tungsten, chromium,

'8 iron, nickel and cobalt with an alkyl ether having from 1 to about 6carbon atoms in each of its alkyl groups heating the resultant mixtureat a temperature less than about 310 C. for a time suiiicient todecompose said organometallic complex, reacting the resulting colloidalsuspension with hydrogen at a temperature in excess of about 225 C. andat a pressure in excess of about 500 p.s.i.g., and recovering theresulting hydrorefined petroleum oil.

9. The process of claim 8 further characterized in that saidorganometallic complex is obtained by the reaction of a covalentmolybdenum halide with said ether.

10. The process of claim 8 further characterized in that saidorganometallic complex is obtained by the reaction of a covalentmolybdenum halide with ethyl ether.

11. The process of claim 8 further characterized in that saidorganometallic complex is obtained by the reaction of a covalentvanadium halide with said ether.

12. The process of claim 8 further characterized in that saidorganometallic complex is obtained by the reaction of a covalentvanadium halide with ethyl ether.

13. A process for hydrorefining a petroleum crude oil which comprisesadmixing said crude oil with an organometallic complex obtained byreacting molybdenum pentachloride and ethyl ether, heating the resultingmixture at a temperature less than about 310 C. for a time sufficient todecompose said organometallic complex, reacting the resulting colloidalsuspension with hydrogen at a temperature of from about 225 C. to about500 C. and at a pressure of from about 500 to about 5000 p.s.i.g., andrecovering a hydrorefined petroleum crude oil.

lid. A process for hydroreiining a petroleum crude oil which comprisesadmixing said crude oil with an organometallic complex obtained byreacting vanadium oxytrichloride and ethyl ether, heating the resultingmixture at a temperature less than about 310 C. for a time sufficient todecompose said organometallic complex, reacting the resulting colloidalsuspension with hydrogen at a temperature of from about 225 C. to about500 C. and at a pressure of from about 500 to about 5000 p.s.i.g., andrecovering a hydrorefined petroleum crude oil.

15. A process for hydrorefining a petroleum crude oil which comprisesadmixing said crude oil with an organometallic complex obtained byreacting molybdenum pentachloride and naphthenic acid, heating theresulting mixture at a temperature less than about 310 C. for a timesuiticient to decompose said organometallic complex, reacting theresulting colloidal suspension with hydrogen at a temperature of fromabout 225 C. to about 500 C. and at a pressure of from about 500 toabout 5000 p.s.i.g., and recovering a hydrorefined petroleum crude oil.

16. A process for hydrorefining a petroleum crude oil which comprisesadmixing said crude oil with an organometallic complex obtained byreacting molybdenum pentachloride and acetone, heating the resultingmixture at a temperature less than about 310 C. for a time sufficient todecompose said organometallic complex, reacting the resulting colloidalsuspension with hydrogen at a temperature of from about 225 C. to about500 C. and at a pressure of from about 500 to about 5000 p.s.i.g., andrecovering a hydrorefined petroleum crude oil.

References Cited by the Examiner UNlTED STATES PATENTS 2,636,841 4/53Mason 208-217 2,999,075 9/61 Pruett 252472 3,006,844 10/61 Limido 2082l73,053,756 9/62 Nottes et a1. 208-189 ALPHONSO D. SULLIVAN, PrimaryExaminer.

1. A CATALYST COMPRISING THE THERMAL DECOMPOSITION PRODUCT OF ANORGANOMETALLIC COMPLEX OBTAINED BY THE REACTION OF HALIDE OF A METALSELECTED FROM THE GROUP CONSISTING OF VANADIUM, NIOBIUM, TANTALUM,MOLYBDENUM, TUNGSTEN, CHROMIUM, IRON, NICKEL AND COBALT WITH AN ALKYLETHER HAVING FROM 1 TO ABOUT 6 CARBON ATOMS IN EACH OF ITS ALKYL GROUPS.8. A PROCESS FOR HYDROREFINING A PETROLEUM OIL WHICH COMPRISES ADMIXINGSAID OIL AND AN ORGANOMETALLIC COMPLEX OBTAINED BY THE REACTION OF ACOVALENT HALIDE OF A METAL SELECTED FROM THE GROUP CONSISTING OFVANADIUM, NIOBIUM, TANTALUM, MOLYBDENUM, TUNGSTEN, CHROMIUM, IRON,NICKEL AND COBALT WITH AN ALKYL ETHER HAVING FROM 1 TO ABOUT 6 CARBONATOMS IN EACH OF ITS ALKYL GROUPS HEATING THE RESULTANT MIXTURE AT ATEMPERATURE LESS THAN ABOUT 310*C. FOR A TIME SUFFICIENT TO DECOMPOSESAID ORGANOMETALLIC COMPLEX, REACTING THE RESULTING COLLOIDAL SUSPENSIONWITH HYDROGEN AT A TEMPERATURE IN EXCESS OF ABOUT 225*C. AND AT APRESSURE IN EXCESS OF ABOUT 500 P.S.I.G., AND RECOVERING THE RESULTINGHYDROREFINED PETROLEUM OIL.